Propionimidate hydrohalides

ABSTRACT

Compounds having the formulae ##STR1## wherein Y is hydroxyl or R 2  O, wherein R 2  is alkyl, aryl or aralkyl, R&#39; is hydrogen, methyl or phenyl and Z is ##STR2## wherein n and m are, individually, 0 or 1, X is a halogen, R 3  is alkyl, hydroxyalkyl, or alkoxyalkyl and R 4 , R 5  and R 6  are, individually, hydrogen, alkyl, aryl, alkaryl or aralkyl, and methods for their production, are disclosed.

This is a division, of application Ser. No. 706,086, filed July 16,1976, now U.S. Pat. No. 4,044,009 which, in turn, is a division ofapplication Ser. No. 467,332, filed May 6, 1974, now U.S. Pat. No.4,007,200.

BACKGROUND OF THE INVENTION

The market for high-efficiency products for use in the treatment ofaqueous suspensions of particulate, solid, water-insoluble materials hasbecome increasing acute in recent years. Industry and research aretherefore continually searching for new systems which can be used tofacilitate the dewatering of aqueous suspensions of organic, or mixturesof organic and inorganic, materials such as distillary wastes,fermentation wastes, wastes from paper manufacturing plants, dye plantwastes and sewage suspensions such as digested sludges, activatedsludges or raw and primary sludges from sewage treatment plants etc.

The most recent and most successful materials used in the treatment ofsuch suspensions have been amidine or, imidazoline polymers, see U.S.Pat. Nos. 3,406,139; 3,666,705; 3,450,646; 3,576,740. These polymers arevery effective materials for use in the treatment of industrial wastes.The polymers are produced, however, by the treatment of correspondingnitrile polymers and are therefore governed in their structure by thestructure of the nitrile polymers. Furthermore, conversion of thenitrile polymers to the imidazoline or amidine polymers does not reach100% and therefore a portion of the resultant imidazoline or amidinepolymer is nonfunctional in its water treating capacity.

Prior attempts to obviate these difficulties have included rearrangementof the groups present in the nitrile charge polymer and the attemptedproduction of unsaturated imidazolines which may be homopolymerized orcopolymerized into more active imidazoline polymers. However, attemptsto produce intermediates, from which the unsaturated imidazolines may beprepared, have proven unsuccessful. Furthermore, attempts to follow theteachings of U.S. Pat. No. 3,210,371 resulted only in the production ofpolymers while the teachings of Oxley et al, Jour. Chem. Soc., 1947,pages 497-503 also resulted in the recovery of polymeric products.

SUMMARY

We have now succeeded in the production of a novel class ofintermediates which can be used to manufacture unsaturated imidazolinemonomers which, in turn, can be homopolymerized and copolymerized intopolymers useful in the treatment of water sludges, the formation offibers and the treatment of paper etc.

DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS

The novel compounds of the present invention have the formulae ##STR3##wherein Y is hydroxyl or R² O, wherein R² is alkyl (C₁ -C₁₀), aryl (C₆-C₁₀) or aralkyl (C₇ -C₁₁), R' is hydrogen, methyl or phenyl and Z is##STR4## wherein n and m, are, individually, 0 or 1, X is a halogen, R³is alkyl (C₁ -C₄), hydroxyalkyl (C₂ -C₄) or alkoxyalkyl (C₂ -C₄) and R⁴,R⁵ and R⁶ are, individually hydrogen, alkyl (C₁ -C₄), aryl (C₆ -C₁₀),aralkyl (C₇ -C₁₁) or alkaryl (C₇ -C₁₁).

The compounds of Formula (C) are prepared by the Pinner reactionaccording to either of the equations: ##STR5## Y, R', R², R³ and X beingas described above.

The reactants are utilized in concentrations such that from aboutequimolar amounts up to an excess of about 10% of the acid per mole ofcyano compound and from about equimolar amounts up to a slight excess ofthe hydroxy (alcohol) compound per mole of the cyano compound areemployed.

The reaction is conducted at a temperature ranging from about -20° C. toabout 30° C., preferably from about -15° C. to about 15° C. Thistemperature range has been found to be successful in preventingextensive side reaction between the acid and the alcohol charges. Thepressure of the reaction zone should be maintained at atmospheric butsubatmospheric or superatmospheric pressures may be used, if desired ornecessary.

The reaction is allowed to proceed for from about 2 to about 72 hours,preferably from about 12 to about 36 hours, in the absence of anycatalytic material. The use of a catalyst is not precluded, however. Thereaction must be conducted under anhydrous conditions in the presence ofan anhydrous solvent. Sufficient solvent to dissolve the chargeingredients is all that is required. Xylene, toluene, benzene, methylenechloride, petroleum ether, ether, dioxane, tetrahydrofuran, aliphatichydrocarbons and the like have been found useful. Also the alcohol (R³OH) may be used as a solvent.

Examples of useful cyano starting compounds in Equations IA and IBinclude β-methoxypropionitrile, β-ethoxypropionitrile,β-butoxypropionitrile, β-octyloxypropionitrile,β-naphthyloxypropionitrile, β-dicycloxypropionitrile,β-phenoxypropionitrile, α-methyl-β-methoxypropionitrile,α-methyl-β-propoxypropionitrile, α-methyl-β-hexoxypropionitrile, acetonecyanohydrin, ethylene cyanohydrin, acetophenone cyanohydrin, and thelike.

The alcohols useful as starting materials in Equations IA and IB in thepresent invention include methanol, ethanol, 1-or 2-hydroxypropane, 1-or 2-hydroxybutane, 1,3-dihydroxybutane, 1,2-dihydroxypropane,1,4-dihydroxybutane, 1,3-dihydroxybutane, 1,2-dihydroxypropane,methoxymethanol, ethoxymethanol, methoxyethanol, 1-methoxy-2-propanol,and the like.

The acidic compounds include hydrochloric acid, hydrofluoric acid,hydrobromic acid and hydroiodic acid.

These compounds of Formula (C) are crystalline and are used to preparethe compounds of Formula (D).

The compounds of Formula (D) wherein m=0 are produced according to theequations: ##STR6##

The compounds of Formula (D) wherein m=1 are produced according to theequations: ##STR7## wherein Y, R', X, R³, R⁴, R⁵, R⁶ and n are asdescribed above.

The reactions of equations IIA and IIB are conducted utilizing at leastabout an 0.5 mole excess of the diamine per mole of HX in the compound(C) charge.

The entire reaction media resulting from the Equation IA or IB reactionsmay be used as a charge to the Equation IIA or IIB reactions or Compound(C) may be isolated, such as by filtration, and used per se as thecharge in the production of Compound (D) where m=0. The IIA and IIBreactions are conducted by adding the excess diamine at the temperatureof the reaction mediae resulting from the Equation IA or IB reactions,with stirring and allowing the resultant media to warm to roomtemperature over a period of from about 1 to about 24 hours. Thereactions are conducted at atmospheric pressure in the presence of thesame solvents as mentioned above, the diamine being added as a solutiontherein. No catalyst need be employed but the conditions must be keptanhydrous, as above.

After the reaction media has reached ambient temperature, the diamine HXcrystals are removed by filtration, centrifugation etc. If desired, theexcess diamine mentioned above may be replaced by an additionalscavenger such as a tertiary amine, e.g. triethylamine. In thisinstance, the diamine reacts only with the Compound (C) charge and thesecondary scavenger picks up the HX released. Other suitable scavengersinclude suitable ion exchangers such as that sold as Amberlyst A21.These secondary scavengers are removed from the reaction media byfiltration etc.

The resultant materials are then used per se without product isolationas the charges to Equations IIIA and IIIB. Compound (D), where m=0, isproduced by heating either charge to about 20° C., but below about 150°C., i.e. below the boiling point of the solvent, while bubbling nitrogengas into the reaction media. This procedure results in the production ofa solvent solution of Compound (D) which is then usually in the presenceof a slight amount of salt or other impurity which, when heated, causethe Compound (D) product to resinify (polymerize). This resinificationcan be prevented by either of two techniques which comprise:

1. Adding an aqueous solution of caustic, which is preferably cold i.e.at about 5° C., shaking the resultant media, allowing the media tosettle into two phases, discarding the water phase, drying the solventphase and distilling off the solvent, or

2. Running the Compound (D) solution through an ion-exchanger which issolvent pretreated with the same solvent in the reaction media and ispreferably macro-reticular. Suitable ion-exchangers include thosementioned above.

When preparing Compound (D) where m=1, the charge ingredients are thesame as those described above for when m=0, however, an excess of thediamine is not employed, nor is any scavenger. As a result, all thediamine reacts with the imidoester and the HX salt portion of thecompound remains as such. Treatment of the Compound (D) HX salt, asdescribed above for resinification prevention with regard to Compound(D) when m=0, results in the removal of the HX portion of the compoundand recovery of the Compound (D), m=0, product.

The compounds of Formula (D), where m=0 or 1, are also crystallinesolids or high boiling liquids.

Examples of suitable diamines which may be used in the Equation IIA,IIB, IVA and IVB reactions include ethylene diamine, propylene diamine,N,N¹ -dimethylpropylene diamine as well as those set forth at column 4,line 60 to column 5, line 2 of U.S. Pat. No. 3,406,139, which patent ishereby incorporated herein by reference.

The compounds of Formula (D) find use primarily in the production oftheir ethylenically unsaturated derivatives, which derivatives may beformed into useful polymers. The unsaturated derivatives are prepared asset forth in our copending application, Ser. No. (Case No. 25,206),filed concurrently herewith, and entitled UNSATURATED IMIDAZOLINES,which application is hereby incorporated herein by reference,

The following examples are set forth for purposes of illustration onlyand are not to be construed as limitations on the present inventionexcept as set forth in the appended claims. All parts and percentagesare by weight unless otherwise specified.

EXAMPLE 1 (Part A)

To a 3-necked reaction vessel equipped with stirrer, gas delivery tube,thermometer and reflux condenser is charged 85.1 parts of3-methoxypropionitrile, 32.0 parts of reagent grade methanol and 300parts of toluene. The exit from the reflux condenser is connected to adrying tower filled with a commercially available drying agent and abath is provided for cooling the vessel below 0° C. Hydrochloric acidgas flow is controlled by means of a rotameter and is passed through acalcium chloride filled trap which serves both as a means for drying thegas and as a receiver in case liquid is sucked back into the line. Aftercharging the reagents and toluene, the solution is stirred and cooled to3° C. and the HCl gas is then fed, while controlling the temperature to-4° to 1° C., until 38.0 parts have been added. The HCl gas is added asrapidly as possible commensurate with complete adsorption and goodtemperature control. The mixture is then stirred for 15 hours in an icebath (maximum 10° C.). Crystals of methyl-3-methoxypropionimidatehydrochloride appear 2.25 hours after the HCl addition is complete. 46.5Hours after the HCl addition is stopped, an 80% yield ofmethyl-3-methoxypropionimidate hydrochloride is formed.

(Part B)

400 Parts of toluene are then added to the reaction media resulting fromPart A at -5° C. over a period of 8 minutes. The solution is cooled to-8° C. and 95.25 parts (molar excess) of dry ethylenediamine, dissolvedin 250 parts of toluene, are added while controlling the temperature to-7° C. to 3° C. The first half of the ethylenediamine is added dropwisedue to the extreme exothermic reaction which takes place. The entireamount of ethylenediamine is added in 17 minutes. The resultant reactionmixture is stirred and warmed to 20° C. over 15 L hours. Highertemperatures (>20° C.) result in a mixture of hydrochlorides beingformed and a corresponding reduction in yield of the desired product.

The ethylenediamine dihydrochloride which forms is then filtered off andwashed three times with toluene. The combined filtrate and washings arethen heated to 47°-57° C. while bubbling nitrogen gas slowly through thevessel until the evolution of ammonia ceases (5 hours) after removingthe calcium chloride drying tower. Care is used to prevent thetemperature from rising above 60° C. since side reactions cause theformation of resinous material.

The resultant solution is then cooled to 5° C. and 100 parts of a cold(5° C.) 30% sodium hydroxide solution are added to extract anyhydrochloric acid remaining. Two phases form, the lower aqueous phase isdiscarded, and the upper toluene phase is dried over 150 parts ofanhydrous potassium carbonate overnight. The potassium carbonate isfiltered off and the filtrate is then added slowly to a heated vacuumdistillation set-up while toluene is continuously distilled off at atemperature of 25°-28° C. Nitrogen gas is continuously passed into thedistillation column. After all the toluene is removed, the pressure isreduced to 0.1 mm Hg. 103 Parts of 2-(2-methoxyethyl)-2-imidazoline witha boiling point of 72°-84° C. and a melting point of 50°-51° C. areremoved.

The 100 MHz 'H NMR spectrum of a CDCl₃ solution (˜5) shows a single peakat 3.58δ due to ring --CH₂ CH₂ -- hydrogens, a sharp single peak at3.26δ due to the methoxy hydrogens and two triplets due to the chain--CH₂ CH₂ -- hydrogens. The triplet belonging to the CH₂ adjacent to themethoxy group is located at 3.61δ; the other CH₂ triplet is at 2.52δ.This latter CH₂ and the ring --CH₂ CH₂ 13 are slightly coupled to eachother, so that one sees evidences of fine structure in those peaks underhigh resolution conditions.

The areas under each of the peaks correspond to the correct numbers ofhydrogens

EXAMPLE 2

To a 3-necked, round-bottomed reaction vessel equipped with stirrer,thermometer, reflux condenser, addition funnel, nitrogen inlet and meansfor cooling, are added 350.0 parts of methylene chloride and 80.0 partsof methyl-3-methoxypropionimidate hydrochloride. The solution is cooledto -4° C. and a solution of 31.25 parts (equimolar amount) ofethylenediamine in 100 parts of methylene chloride are added at a ratesuch that the temperature remains between -4° C. and -8° C. Theresultant solution is then stirred overnight and allowed to warm to roomtemperature. Stirring is continued, nitrogen gas is bubbled through thereaction media and the mixture is heated to reflux until ammoniaevolution ceases. After filtration, washing and drying, 74.0 parts ofwaxy, crystalline material is obtained. Two recrystallizations, one fromalcohol ether and one from 1,2-dichloroethane give a material having amelting point of 102°-104° C. identified as2-(2-methoxyethyl)-2-imidazoline hydrochloride by IR spectrum and NMR.During the recrystallizations, ethylenediamine dihydrochloride isfiltered off and identified.

The 100 MHz 'H NMR spectrum of a DMSO-d₆ solution (˜5%) shows a sharpsingle peak at 3.81 δ due to the ring --CH₂ CH₂ -- hydrogens, a sharpsingle peak at 3.26 δ due to the methoxy hydrogens, and two triplets dueto the chain --CH₂ CH₂ -- hydrogens. The triplet belonging to the CH₂adjacent to the methoxy group is located at 3.68 δ; the other CH₂triplet is at 2.79 δ. The areas under each of the peaks correspond tothe correct numbers of hydrogens.

EXAMPLE 3

100 Parts of 6N sodium hydrochloride in a suitable reaction vessel arecooled to 5° C with an ice-water bath and 22.7 parts of the2-(2-methoxyethyl)-2-imidazoline hydrochloride of Example 2 are added tothe cold solution. An oil separates. The contents of the vessel aretransferred to a separatory vessel and the aqueous phase is extractedfour times with 30 parts of reagent grade tetrahydrofuran. The combinedtetrahydrofuran extracts are dried over anhydrous potassium carbonatefor 15 hours. The potassium carbonate is then filtered off and thetetrahydrofuran solution is distilled to yield 14.0 parts of2-(2-methoxyethyl)-2-imidazoline.

EXAMPLES 4-17

Following the procedures of Example 1, Part A, various cyano compoundsare reacted with various alcohols in the presence of various acids inaccordance with Equations IA and IB, above. The charge materials usedand the resultant products are set forth in Table I, below.

                                      TABLE I                                     __________________________________________________________________________    Charge According to Equations IA or IB                                        Example                                                                            Y     R'  R.sup.3                                                                              X  Product                                              __________________________________________________________________________     4   C.sub.2 H.sub.5 O                                                                   H   C.sub.2 H.sub.5                                                                      Cl Ethyl-3-ethoxypropionimidate                                                  hydrochloride                                         5   C.sub.4 H.sub.9 O                                                                   H   C.sub.4 H.sub.9                                                                      Br n-butyl-3-n-butoxypropionimidate                                              hydrobromide                                         6    C.sub.6 H.sub.13 O                                                                  CH.sub.3                                                                          C.sub.2 H.sub.4 OH                                                                   Br 2-hydroxyethyl-3-(hexyloxy)-2-methyl-                                         propionimidate hydrobromide                           7   C.sub.2 H.sub.5 O                                                                   H   CH.sub.3                                                                             Cl Methyl-3-ethoxypropionimidate                                                 hydrochloride                                         8   C.sub.3 H.sub.7 O                                                                   H   3-C.sub.4 H.sub.8 OH                                                                 Br 3-hydroxybutyl-3-isopropoxypropion-                                           imidate hydrobromide                                  9   C.sub.10 H.sub.21 O                                                                 CH.sub.3                                                                          CH.sub.3 OCH.sub.2                                                                   F  Methoxymethyl-3-(decyloxy)-2-methyl-                                          propinimidate hydrofluoride                          10   CH.sub.3 O                                                                          H   C.sub.2 H.sub.5                                                                      Cl Ethyl-3-methoxypropionimidate                                                 hydrochloride                                        11   C.sub.10 H.sub.21 O                                                                 CH.sub.3                                                                          C.sub.2 H.sub.5 OC.sub.2 H.sub.4                                                     I  2-ethoxyethyl-3-(decyloxy)-2-                                                 methylpropionimidate hydriodide                      12   --    H   C.sub.2 H.sub.5                                                                      Br Ethyl lactimidate hydrobromide                       13   OH    H   CH.sub.3                                                                             Cl Methyl-2-methyllactimidate                                                    hydrochloride                                        14   OH    H   CH.sub.3                                                                             Cl Methyl hydracrylimidate                                                       hydrochloride                                        15   --    C.sub.6 H.sub.5                                                                   C.sub.3 H.sub.7                                                                      F  Propyl-α-methylmandelimidate                                            hydrofluoride                                        16   OH    CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                    Cl Isopropyl-2-methylhydracrylimidate                                            hydrochloride                                        17   OH    C.sub.6 H.sub.5                                                                   i-C.sub.3 H.sub.7                                                                    Cl Isopropyl tropimidate                                                         hydrochloride                                        __________________________________________________________________________

EXAMPLES 18-32

Following the procedure of Example 1, Part B, the imidates of Examples4-17 are converted to their corresponding imidazolines ortetrahydropryrimidines in accordance with Equations IIA, IIB, IIIA andIIIB, above. The results are set forth in Table II, below.

                                      TABLE II                                    __________________________________________________________________________    Imidate Of  Diamine                                                           Example                                                                            Example No.                                                                          R.sup.6                                                                           R.sup.5                                                                          R.sup.4                                                                          n Product                                               __________________________________________________________________________    18    4     H   H  CH.sub.3                                                                         O 2-(2-ethoxyethyl)-4(or 5)-                                                    methyl-2-imidazoline                                  19   5      H   C.sub.6 H.sub.5                                                                  H  O 2-(2-butoxyethyl()-4(or 5)-                                                   phenyl-2-imidazoline                                  20    6     C.sub.4 H.sub.9                                                                   H  CH.sub.3                                                                         O 1-butyl-2-[2-(hexyloxy)-1-                                                    methylethyl]-4(or 5)-methyl-                                                  2-imidazoline                                         21    7     H   H  C.sub.2 H.sub.5                                                                  1 2-(2-ethoxyethyl)-4-ethyl-                                                    1,4,5,6-tetrahydropyrimidine                          22    8     C.sub.7 H.sub.7                                                                   H  H  O 2-(2-isopropoxyethyl)-1-O                                                     (m or p)-tolyl-2-imidazoline                          23    9     H   CH.sub.3                                                                         CH.sub.3                                                                         O 2-[2-decyloxy)-1-methyl-                                                      ethyl]-4,5-dimethyl-2-                                                        imidazoline                                           24   10     C.sub.10 H.sub.7                                                                  H  H  1 2-(2-methoxyethyl)-1-[1 (or                                                   2)-naphthyl]-1,4,5,6-tetra-                                                   hydropyrimidine                                       25   11     H   C.sub.7 H.sub.7                                                                  H  O 4 (or 5)-benzyl-2-[2-(decyloxy)-                                              1-methylethyl]-2-imidazoline                          26   12     H   H  H  O α-methyl-2-imidizoline-2-methanol               27   13     H   H  H  O α,α-dimethyl-2-imidazoline-2-                                     methanol                                              28   14     H   H  H  O 2-imidazoline-2-ethanol                               29   15     H   H  H  O α-methyl-α-phenyl-2-imidazoline-                                  2-methanol                                            30   15     H   H  H  1 1,4,5,6-tetrahydro-α-methyl-α-                                    phenyl-2-pyrimidinemethanol                           31   16     H   H  H  O α-methyl-2-imidazoline-2-                                               ethanol                                               32   17     H   H  H  1 1,4,5,6-tetrahydro-α-phenyl-2-                                          pyrimidineethanol                                     __________________________________________________________________________

EXAMPLES 33-41

Following the procedure of Example 2, various of the imidates ofExamples 4-17 are converted to their corresponding imidazoline ortetrahydropyrimidine hydrohalides in accordance with Equations IVA andIVB, above. The results are set forth in Table III, below.

                                      TABLE III                                   __________________________________________________________________________    Imidate Of  Diamine                                                           Example                                                                            Example No.                                                                          R.sup.6                                                                           R.sup.5                                                                          R.sup.4                                                                          n Product                                               __________________________________________________________________________    33   4      H   H  CH.sub.3                                                                         O 2-(2-ethoxyethyl)-4 (or 5)-                                                   methyl-2-imidazoline hydrochlo-                                               ride                                                  34   6      H   H  C.sub.2 H.sub.5                                                                  1 4-ethyl-2-[2-(hexyloxy)-1-                                                    methylethyl]-1,4,5,6-tetrahydro-                                              pyrimidine hydrochloride                              35   7      H   C.sub.6 H.sub.5                                                                  H  O 2-(2-ethoxyethyl)-4 (or 5)-                                                   phenyl-2-imidazoline hydro-                                                   chloride                                              36   9      C.sub.7 H.sub.7                                                                   H  H  O 1-benzyl-2-[2-(decyloxy)-1-                                                   methylethyl]-2-imidazoline                                                    hydrochloride                                         37   10     C.sub.10 H.sub.7                                                                  H  H  1 1,4,5,6-tetrahydro-2-(2-methoxy-                                              ethyl)-1-(1-naphthyl) pyrimidine                                              hydrochloride                                         38   11     H   C.sub.7 H.sub.7                                                                  H  O 2-[2-(decyloxy)-1-methylethyl]-                                               4 (or 5)-p-tolyl-2-imidazoline                                                hydrochloride                                         39   12     H   H  H  O α-methyl-2-imidaxoline-2-                                               methanol hydrochloride                                40   13     H   H  H  1 1,4,5,6-tetrahydro-α,α-dimethyl-                                  2-pyrimidine hydrochloride                            41   15     H   H  CH.sub.3                                                                         O α,4 (or 5)-dimethyl-α-dimethyl-                                   2-imidazoline-2-methanol                                                      hydrochloride                                         __________________________________________________________________________

EXAMPLES 42-50

The procedure of Example 3 is again followed except that the products ofExamples 33-41 are used as charge materials. In each instance, thehydrohalides are converted to their corresponding imidazolines.

We claim:
 1. A compound having the formula ##STR8## wherein Y is R² O,R² being alkyl (C₁ -C₁₀), aryl (C₈ -C₁₀) or aralkyl (C₇ -C₁₁), R¹ ishydrogen, methyl or phenyl and Q is ##STR9## wherein R³ is alkyl (C₁-C₄), hydroxyalkyl (C₂ -C₄) or alkoxyalkyl (C₂ -C₄) and X is a halogen.2. A compound according to the claim 1 wherein Y is methoxy, R¹ ishydrogen, X is chlorine and R³ is methyl.
 3. A compound according toclaim 1 wherein Y is ethoxy, R¹ is hydrogen, X is chlorine and R³ isethyl.
 4. A compound according to claim 1 wherein Y is ethoxy.
 5. Acompound according to claim 1 wherein R³ is ethyl.
 6. A compoundaccording to claim 1 wherein R¹ is methyl.